Tempered glass and glass

ABSTRACT

A tempered glass of the present invention includes, as a glass composition, in terms of mass %, 45 to 75% of SiO 2 , 0 to 30% of Al 2 O 3 , and 0 to 30% of Li 2 O+Na 2 O+K 2 O and has a β-OH value of 0.3 to 1/mm.

TECHNICAL FIELD

The present invention relates to a tempered glass, and morespecifically, to a tempered glass which is suitable for exterior partsfor a mobile PC and the like. The present invention also relates to aglass, and more specifically, to a glass for tempering which is suitablefor exterior parts for a mobile PC and the like.

BACKGROUND ART

Mobile phones equipped with a touch panel have been widely used, and aglass tempered by an ion exchange or the like (so-called tempered glass)tends to be used for the cover glass of mobile phones. Because atempered glass is high in mechanical strength compared with anuntempered glass, the tempered glass is suitable for the above-mentionedapplication (see Patent Document 1 and Non-patent Document 1 below).

In recent years, touch panels are being equipped for applications otherthan mobile phones as well, and hence, exterior parts each having aspecific shape such as a curved shape are necessary depending on theirapplications. In order to adopt a tempered glass to those applications,it is necessary to subject the tempered glass to processing so that thetempered glass has a specific shape such as a curved shape. A temperedglass having a specific shape can be produced by forming molten glassinto obtain a glass having, for example, a plate shape, then modifyingthe shape of the glass to a specific shape by thermal processing, and,after that, performing a tempering treatment (see Patent Documents 2 and3 below).

Thus, those tempered glasses are required to have characteristics suchas excellent thermal processability, that is, a low softening point, aswell as a high mechanical strength.

-   Patent Document 1: JP 2006-83045 A-   Patent Document 2: U.S. Pat. No. 7,168,047-   Patent Document 3: JP 2001-247342 A-   Non-patent Document 1: Tetsuro Izumitani et al., “New glass and    physical properties thereof”, First edition, Management System    Laboratory. Co., Ltd., Aug. 20, 1984, pp. 451-498

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

The mechanical strength of a tempered glass can be enhanced byincreasing the compression stress value of a compression stress layerformed on its surface and increasing the thickness of the compressionstress layer.

However, it is difficult to lower a softening point while thecompression stress value of a compression stress layer is increased andwhile the thickness of the compression stress layer is increased. Inorder that while the compression stress value of a compression stresslayer is increased, the thickness of the compression stress layer isincreased, it is necessary to introduce Al₂O₃ and the like, which arecomponents for enhancing ion exchange performance, in a glasscomposition, because the introduction of those elements raises asoftening point.

Thus, a technical object of the present invention is to provide atempered glass having a specific shape such as a curved shape bycreating a tempered glass having a low softening point while having ahigh mechanical strength.

Means for Solving the Problem

The inventors of the present invention have studied in various ways andfound that the appropriate control of a β-OH value results in loweringof softening point, while securing an appropriate compression stressvalue and thickness of compression stress layer. Thus, the inventorspropose the finding as the present invention. That is, the temperedglass of the present invention is characterized by including, as a glasscomposition, in terms of mass %, 45 to 75% of SiO₂, 0 to 30% of Al₂O₃,and 0 to 30% of Li₂O+Na₂O+K₂O and having a β-OH value of 0.3 to 1/mm.Here, the term “β-OH value” refers to a value obtained from thefollowing equation 1 by measuring the transmittance of the glass byFT-IR.

β-OH value=(1/X)log 10(T ₁ /T ₂)  (Equation 1)

X: thickness of glass (mm)T₁: transmittance (%) at a reference wavelength of 3846 cm⁻¹T₂: minimum transmittance (%) at a hydroxyl group absorption wavelengthof around 3500 cm⁻¹

The β-OH value can be increased by, for example, (1) selecting a rawmaterial having a high water content (for example, a hydroxide rawmaterial), (2) adding water to the raw material, (3) reducing theaddition amount of a component (such as Cl or SO₃) which reduces thewater content in the glass, or not using such the component, (4)employing oxygen combustion during melting or introducing steam directlyinto a melting furnace to increase the water content in the atmospherein the furnace, (5) carrying out steam bubbling in the molten glass, (6)using a large-sized melting furnace to melt the glass, or (7) decreasingthe flow rate of the molten glass.

The tempered glass of the present invention can include, as a glasscomposition, 0.1 mass % or more of Li₂O+Na₂O+K₂O.

The tempered glass of the present invention can further include, as aglass composition, 0 to 5 mass % of B₂O₃.

The tempered glass of the present invention is preferable to includingsuch a compression stress layer on the surface in that a compressionstress value of the compression stress layer is 50 MPa or more, and athickness of the compression stress layer is 10 μm or more. Here, theterms “compression stress value of a compression stress layer” and“thickness of a compression stress layer” refer to values obtained byobserving the number of interference fringes and the intervals betweenthe fringes by using a surface stress meter to calculate the compressionstress value on the surface and the thickness.

The tempered glass of the present invention is preferable to having asoftening point of 900° C. or less. Here, the term “softening point”refers to a value measured based on a method of ASTM C338.

The tempered glass of the present invention is preferable to having astrain point of 400° C. or more. Here, the term “strain point” refers toa value measured based on a method according to ASTM C336.

The tempered glass of the present invention is preferable to having aliquidus temperature of 1200° C. or less. Here, the term “liquidustemperature” refers to a value obtained by pulverizing the glass,placing the glass powder passing through a standard sieve of 30 mesh(mesh opening 500 μm) and remaining on 50 mesh (mesh opening 300 μm) ina platinum boat, keeping the glass powder in a temperature gradientfurnace for 24 hours, and measuring a temperature at which a crystal isdeposited.

The tempered glass of the present invention is preferable to having aliquidus viscosity of 10⁴ dPa·s or more. Here, the term “liquidusviscosity” refers to a value obtained by measuring the viscosity of aglass at the liquidus temperature by a platinum sphere pull up method.

The tempered glass of the present invention is preferable to having athermal expansion coefficient of 50 to 110×10⁻⁷/° C. Here, the term“thermal expansion coefficient” refers to a value measured by using adilatometer and shows an average value in the temperature range of from30 to 380° C.

The tempered glass of the present invention can be formed by subjectinga glass having a plate shape to thermal processing. Here, the term“thermal processing” includes the case where molten glass is directlyformed into a specific shape by press molding or the like.

The tempered glass of the present invention may have a shape other thana plate shape.

The glass of the present invention is characterized by including, as aglass composition, in terms of mass %, 45 to 75% of SiO₂, 0 to 30% ofAl₂O₃, and 0 to 30% of Li₂O+Na₂O+K₂O, and having a β-OH value of 0.3 to1/mm.

The glass of the present invention can include, as a glass composition,0.1 mass % or more of Li₂O+Na₂O+K₂O.

The glass of the present invention can further include, as a glasscomposition, 0 to 5 mass % of B₂O₃.

The glass of the present invention is preferable to having a softeningpoint of 900° C. or less.

The glass of the present invention is preferable to having a strainpoint of 400° C. or more.

The glass of the present invention is preferable to having a liquidustemperature of 1200° C. or less.

The glass of the present invention is preferable to having a liquidusviscosity of 10⁴ dPa·s or more.

The glass of the present invention is preferable to having a thermalexpansion coefficient of 50 to 110×10⁻⁷/° C.

The glass of the present invention may have been subjected to thermalprocessing.

The glass of the present invention may have a shape other than a plateshape.

DESCRIPTION OF EMBODIMENTS

A method of forming a compression stress layer on the surface of a glassincludes a physical tempering method and a chemical tempering method.For the tempered glass of the present invention, a compression stresslayer is preferable to being formed by a chemical tempering method. Thechemical tempering method is a method of introducing an alkali ionhaving a large ion radius onto the surface of a glass by an ion exchangeat a temperature equal to or less than a strain point. When acompression stress layer is formed by the chemical tempering method, anion exchange treatment can be performed successfully even if thethickness of the glass is small, and desired mechanical strength can beobtained. Further, when a compression stress layer is formed by thechemical tempering method, the tempered glass is hardly broken easilyeven if the tempered glass is cut after a tempering treatment, which isdifferent from the case of a physical tempering method such as an aircooling tempering method.

For producing the tempered glass, a tempering treatment needs to beperformed after molten glass is formed into a predetermined shape. It isdesirable that the tempering treatment be performed by an ion exchangetreatment as described above. The ion exchange treatment can beperformed, for example, by immersing the glass in a potassium nitratesolution at 400 to 550° C. for 1 to 8 hours. It is desirable thatoptimum ion exchange conditions be selected in view of the viscosityproperty, application, and plate thickness of the glass, tensile stressin the glass, and the like.

In the tempered glass of the present invention, the lower range of aβ-OH value is preferably 0.3/mm or more, more preferably 0.32/mm ormore, 0.34/mm or more, 0.35/mm or more, 0.4/mm or more, 0.45/mm or more,0.5/mm or more, or 0.55/mm or more, or particularly preferably 0.6/mm ormore, and the upper range of the β-OH value is preferably 1/mm or less,more preferably 0.9/mm or less or 0.8/mm or less, or particularlypreferably 0.7/mm or less. When the β-OH value is less than 0.3/mm,lowering a softening point becomes difficult, resulting in a difficultyin performing thermal processing, or even if thermal processing isperformed, loading on a mold becomes large, and hence, the life time ofthe mold is shortened. As a result, production cost of the temperedglass is largely increased. On the other hand, when the β-OH value ismore than 1/mm, the network structure of glass is readily damaged,resulting in easy alleviation of stress, and hence, enhancing themechanical strength of the tempered glass becomes difficult. That is,when the network structure of glass is damaged, the compression stressof the compression stress layer is easily relaxed during an ion exchangetreatment, resulting in a difficulty in increasing the compressionstress value of the compression stress layer.

In the tempered glass of the present invention, it is preferred thataluminum hydroxide, hydrous zirconium oxide, and the like be used. Ifthose are used, the β-OH value can be increased while the dissolvabilityof a glass batch is promoted. Improving ion exchange performancerequires much use of materials poorly dissolved such as Al₂O₃, ZrO₂, andTiO₂, but when those materials are used in large amounts, Al₂O₃ poorlydissolved and the like easily flow out as undissolved glass stones.However, when aluminum hydroxide, hydrous zirconium oxide, and the likeare used, the dissolvability of a glass batch can be enhanced, andhence, production of undissolved glass stones of Al₂O₃ poorly dissolvedand the like can be prevented.

In the tempered glass of the present invention, the compression stressvalue of the compression stress layer is preferably 50 MPa or more, 100MPa or more, 300 MPa or more, 500 MPa or more, 600 MPa or more, andparticularly preferably 700 MPa or more. As the compression stress valueof the compression stress layer increases, the mechanical strength ofthe tempered glass becomes higher. Meanwhile, when extremely largecompression stress is generated on the surface, a micro-crack isproduced on the surface, with the result that the mechanical strength ofthe tempered glass may be reduced adversely. Further, when extremelylarge compression stress is generated on the surface, tensile stress inthe glass may become extremely high. Therefore, the compression stressof the compression stress layer is preferably set to 1300 MPa or less.It should be noted that the compression stress value of the compressionstress layer may be increased by increasing the contents of Al₂O₃, TiO₂,ZrO₂, MgO, and ZnO, decreasing the contents of SrO and BaO, shorteningthe ion exchange time, or reducing the ion exchange temperature.

When the tempered glass is mounted on a touch panel, end users haveincreased chances of touching the surface of the tempered glass withtheir fingers, and hence, the mechanical strength of the tempered glasstend to decrease due to flaws on the surface and the like. In order tomaintain the mechanical strength of the tempered glass, increasing thethickness of the compression stress layer is effective. In the temperedglass of the present invention, the thickness of the compression stresslayer is preferably 10 μm or more, 20 μm or more, 30 μm or more, 40 μmor more, or 50 μm or more, or particularly preferably 60 μm or more. Asthe thickness of the compression stress layer is larger, the temperedglass is more difficult to break even if the tempered glass has a deepflaw. On the other hand, when the thickness of the compression stresslayer is too large, cutting and processing the tempered glass becomemore difficult. Therefore, the thickness of the compression stress layeris preferably 200 μm or less. It should be noted that the thickness ofthe compression stress layer may be increased by increasing the contentsof Al₂O₃, K₂O, TiO₂, ZrO₂, MgO, and ZnO, decreasing the contents of SrOand BaO, lengthening the ion exchange time, or raising the ion exchangetemperature.

In the tempered glass of the present invention, the tensile stress valuein the glass calculated with the following mathematical equation 2 ispreferably 200 MPa or less, 150 MPa or less, 100 MPa or less, orparticularly 50 MPa or less. As the tensile stress value in the glassbecomes smaller, the probability that the tempered glass is broken dueto a defect in the glass becomes lower. However, when the tensile stressvalue in the glass is set to be extremely small, the compression stressvalue and thickness of the compression stress layer on the surfacebecome small. Therefore, the tensile stress value in the glass ispreferably 1 MPa or more, 10 MPa or more, or particularly preferably 15MPa or more.

Tensile stress value in glass=(compression stress value of compressionstress layer×thickness of compression stress layer)/(thickness oftempered glass−thickness of compression stress layer×2)  (Equation 2)

The tempered glass of the present invention contains, as a glasscomposition, in terms of mass %, 45 to 75% of SiO₂, 0 to 30% of Al₂O₃,and 0 to 30% of Li₂O+Na₂O+K₂O. In the tempered glass of the presentinvention, the reason that the glass composition is limited to the aboveis given below.

SiO₂ is a component for forming a network of the glass, and the contentis 45 to 75%, preferably 50 to 70%, more preferably 50 to 63%, stillmore preferably 52 to 63%, particularly preferably 52 to 60%. When thecontent of SiO₂ is too large, meltability and formability of the glassdecrease, and, in addition, the thermal expansion coefficient becomestoo small, and matching of the thermal expansion coefficient with thoseof peripheral materials becomes difficult. On the other hand, when thecontent of SiO₂ is too small, glass formation becomes difficult.Further, the thermal expansion coefficient becomes too high, and thethermal shock resistance of the glass tends to lower.

Al₂O₃ is a component for enhancing ion exchange performance, also has aneffect of enhancing the strain point and the Young's modulus, and thecontent is 0 to 30%. When the content of Al₂O₃ is too large, adevitrified crystal tends to deposit in the glass, and the formabilitytends to be low and in particular, it becomes difficult to form a glasshaving a plate shape by an overflow down draw method and the like.Further, when the content of Al₂O₃ is too large, the thermal expansioncoefficient becomes too small, matching of the thermal expansioncoefficient with those of peripheral materials becomes difficult, andthe viscosity becomes too high, with the result that it becomesdifficult to melt the glass. In addition, the softening point becomestoo high, the temperature for thermal processing becomes too high, andin particular, the temperature during the press molding becomes toohigh. Therefore, the deterioration of a mold may be accelerated. On theother hand, when the content of Al₂O₃ is too small, the ion exchangeperformance may not be exhibited sufficiently. Comprehensivelyunderstanding the above-mentioned viewpoints, the upper range of Al₂O₃is preferably 25% or less, 23% or less, 22% or less, 20% or less, 19% orless, 18% or less, or 17% or less, or particularly preferably 16.5% orless. The lower range of Al₂O₃ is preferably 3% or more, 5% or more, 10%or more, 12% or more, or 13% or more, or particularly preferably 14% ormore.

Li₂O+Na₂O+K₂O is an ion exchange component, and also is a component forlowering the viscosity to improve the meltability and the formability.When the content of Li₂O+Na₂O+K₂O is too large, the glass tends to bedevitrified. In addition, the thermal expansion coefficient increasestoo much, and hence, the thermal shock resistance lowers, and matchingof the thermal expansion coefficient with those of peripheral materialsbecomes difficult. Further, when the content of Li₂O+Na₂O+K₂O is toolarge, the strain point decreases too much, and thus, the compressionstress value may be hardly increased. In addition, when the content ofLi₂O+Na₂O+K₂O is too large, the viscosity at around the liquidustemperature lowers, whereby it may be difficult to ensure a highliquidus viscosity. Therefore, the content of Li₂O+Na₂O+K₂O ispreferably 30% or less, 25% or less, or particularly preferably 20% orless. On the other hand, when the content of Li₂O+Na₂O+K₂O is too small,the ion exchange performance and the meltability may decrease, and thesoftening point may become unreasonably high. Therefore, the content ofLi₂O+Na₂O+K₂O is preferably 0.1% or more, 8% or more, 10% or more, or13% or more, or particularly 15% or more.

Li₂O is an ion exchange component, which also lowers the viscosity toimprove the meltability and the formability. Further, Li₂O is acomponent for enhancing the Young's modulus. In addition, Li₂O has ahigh effect of enhancing the compression stress value, among alkalimetal oxides. However, when the content of Li₂O is too large, theliquidus viscosity lowers and the glass tends to be devitrified, and, inaddition, the thermal expansion coefficient increases too much, andhence, the thermal shock resistance lowers and matching of the thermalexpansion coefficient with those of peripheral materials becomesdifficult. Further, when the content of Li₂O is too large, thelow-temperature viscosity, and in particular, strain point lower toomuch, and hence, stress relaxation tends to occur, and the compressionstress value, on the contrary, lowers in some cases. Thus, the contentof Li₂O is preferably 0 to 10%, 0 to 8%, 0 to 6%, 0 to 4%, 0 to 3%, 0 to2%, 0 to 1%, or 0 to 0.5%, or particularly preferably 0 to 0.1%.

Na₂O is an ion exchange component, which also lowers the viscosity toimprove the meltability and the formability and improve thedevitrification resistance. The content of Na₂O is preferably 0 to 20%,8 to 16%, 8 to 15%, 9 to 15%, 10 to 15%, or 11 to 15%, or particularlypreferably 12 to 15%. When the content of Na₂O is too large, the thermalexpansion coefficient becomes too large, and hence, the thermal shockresistance lowers, and matching of the thermal expansion coefficientwith those of peripheral materials becomes difficult. In addition, whenthe content of Na₂O is too large, the strain point lowers and a balanceof the glass composition is deteriorated, with the result that, on thecontrary, the devitrification resistance tends to be deteriorated. Onthe other hand, when the content of Na₂O is too small, the meltabilitylowers, the thermal expansion coefficient lowers too much, and the ionexchange performance tends to be deteriorated.

K₂O is a component for enhancing ion exchange performance, and shows ahigh effect of increasing the thickness of a compression stress layer,among alkali metal oxides. In addition, K₂O is a component for loweringthe viscosity to enhance the meltability and the formability. Further,K₂O is also a component for improving the denitrification resistance.When the content of K₂O is too large, the thermal expansion coefficientbecomes too large, and hence, the thermal shock resistance lowers, andmatching of the thermal expansion coefficient with those of peripheralmaterials becomes difficult. Further, when the content of K₂O is toolarge, there are tendencies that the strain point lowers, and a balanceof the glass composition is deteriorated, with the result that, on thecontrary, the denitrification resistance tends to be deteriorated.Taking the above points into consideration, the content of K₂O ispreferably 0 to 10% and the upper range of the K₂O is preferably 8% orless, 7% or less, or 6% or less, or particularly preferably 5% or less.Taking the thickness of the compression stress layer into consideration,the lower range of K₂O is preferably 0.1% or more, 0.5% or more, or 1%or more, or particularly preferably 2% or more.

In addition to the above components, the following components can beadded to the glass composition.

B₂O₃ is a component that has the effects of reducing the liquidustemperature, viscosity, and density and improves ion exchangeperformance, especially the compression stress value. The content ofB₂O₃ is preferably 0 to 10%, 0 to 5%, or 0 to 3%, or particularlypreferably 0 to 2%. When the content of B₂O₃ is excessive, the surfacemay be stained by an ion exchange, the water resistance may degrade, orthe liquidus viscosity may lower. In particular, when alkali metaloxides are incorporated into the glass composition in the tempered glassof the present invention, the excessive content of B₂O₃ results inremarkable erosion of a refractory in a melting furnace by the B₂O₃component and alkali component in the glass during a melting process. Asa result, the life time of a furnace may be shortened. Further, theexcessive content of B₂O₃ results in the tendency of a smaller thicknessof a compression stress layer.

MgO+CaO+SrO+BaO (total content of MgO, CaO, SrO, and BaO) is a componentfor reducing the viscosity to improve the meltability and formabilityand increasing the strain point or Young's modulus. The content ofMgO+CaO+SrO+BaO is preferably 0 to 15%, 0 to 10%, or 0 to 6%, orparticularly 0 to 5%. However, when the total content of MgO+CaO+SrO+BaOis too large, the density or thermal expansion coefficient becomes toohigh, the denitrification resistance degrades, and the ion exchangeperformance is apt to lower.

MgO is a component which lowers the viscosity to enhance the meltabilityand the formability, or to enhance the strain point and the Young'smodulus, and particularly shows a high effect of improving the ionexchange performance, among alkali earth metal oxides. The content ofMgO is preferably 0 to 10%, 0 to 6%, or 0 to 4%, or particularlypreferably 0 to 3%. However, when the content of MgO is too large, thedensity and the thermal expansion coefficient becomes too high, and theglass tends to be devitrified.

CaO is a component which lowers the viscosity to enhance the meltabilityand the formability, or to enhance the strain point and the Young'smodulus, and particularly shows a high effect of improving the ionexchange performance, among alkali earth metal oxides. The content ofCaO is preferably 0 to 10%, 0 to 8%, or 0 to 6%, and particularlypreferably 0 to 3%. However, when the content of CaO is too large, thedensity and the thermal expansion coefficient becomes too high, theglass tends to be devitrified, and the balance of the glass compositionmay deteriorate, and on the contrary, the ion exchange performancedeteriorates in some cases.

When the content of SrO+BaO (total content of SrO and BaO) is preferably0 to 5%, 0 to 3%, 0 to 2.5%, 0 to 2%, or 0 to 1%, or particularlypreferably 0 to 0.1%. When the content of SrO+BaO is limited to theabove range, the ion exchange performance is effectively improved. Itshould be noted that, because SrO+BaO has the function of inhibiting anion exchange reaction, when the content of SrO+BaO is excessively high,the mechanical strength of the tempered glass is hardly increased.

SrO is a component that lowers the viscosity to enhance the meltabilityand formability or to enhance the strain point and Young's modulus, andthe content thereof is preferably 0 to 5%. BaO is a component thatlowers the viscosity to enhance the meltability and formability or toenhance the strain point and Young's modulus, and the content thereof ispreferably 0 to 5%. When the content of SrO or BaO is too large, the ionexchange performance tends to deteriorate. Further, the density and thethermal expansion coefficient become too large, and the glass tends tobe devitrified. In particular, the content of SrO is desirably 3% orless, 2% or less, 1% or less, or 0.5% or less, or particularly desirably0.1% or less. Further, the content of BaO is desirably 3% or less, 2% orless, 1% or less, 0.8% or less, or 0.5% or less, or particularlydesirably 0.1% or less.

When the value obtained by dividing the total content of MgO+CaO+SrO+BaOby the total content of Li₂O+Na₂O+K₂O, that is, the value(MgO+CaO+SrO+BaO)/(Li₂O+Na₂O+K₂O) is large, the denitrificationresistance tends to be deteriorated. Therefore, the value(MgO+CaO+SrO+BaO)/(Li₂O+Na₂O+K₂O) is preferably 0.5 or less or 0.4 orless, or particularly preferably 0.3 or less.

ZnO is a component which improves the ion exchange performance, and inparticular, component which enhances the compression stress value.Further, ZnO is a component which lowers the viscosity without loweringthe low-temperature viscosity, and the content thereof is preferably 0to 10%, 0 to 5%, or 0 to 3%, or particularly preferably 0 to 1%.However, when the content of ZnO becomes too large, the glass manifestsphase separation, the devitrification resistance lowers, and the densityis apt to become large.

ZrO₂ is a component for improving the ion exchange performance markedlyand increasing the viscosity around the liquidus viscosity and strainpoint. The content of ZrO₂ is preferably 0 to 10%, 0 to 9%, 0.001 to 8%,0.01 to 7%, 1 to 7%, 2 to 7%, or 3 to 6%, or particularly preferably 3to 5%. When the content of ZrO₂ is too high, the devitrificationresistance may lower extremely.

TiO₂ is a component for improving the ion exchange performance andreducing the viscosity. When the content of TiO₂ is too high, the glassis colored or the devitrification resistance lowers. Therefore, thecontent of TiO₂ is preferably 1% or less or 0.5% or less, orparticularly preferably 0.1% or less.

P₂O₅ is a component which improves the ion exchange performance, and inparticular, a component which increases the thickness of the compressionstress layer, and the content thereof is preferably 0 to 8%, 5% or less,4% or less, 2% or less, or 0.5% or less, or particularly preferably 0.1%or less. However, when the content of P₂O₅ is too large, the glassdevelops phase separation, and the water resistance is apt to belowered.

As a fining agent, one kind or two or more kinds selected from the groupconsisting of As₂O₃, Sb₂O₃, CeO₂, SnO₂, F, Cl, and SO₃ may be added inan amount of 0 to 3%. It should be noted that it is preferred, whenpossible, to refrain from the use of As₂O₃, Sb₂O₃, and F, in particular,As₂O₃ and Sb₂O₃ in view of environment aspect, and each content thereofis preferably less than 0.1%. SnO₂, SO₃, and Cl are preferred finingagents. The content of SnO₂ is preferably 0 to 1% or 0.01 to 0.5%, orparticularly preferably 0.05 to 0.4%. When the content of SnO₂ is morethan 1%, the denitrification resistance easily lowers. The content ofSO₃ is preferably 0 to 0.1%, 0.0001 to 0.1%, 0.0003 to 0.08%, or 0.0005to 0.05%, or particularly preferably 0.001 to 0.03%. When the content ofSO₃ is more than 0.1%, SO₃ reboils during the melting process, therebyquality in bubble existing in glass tends to be deteriorated. Thecontent of Cl is preferably 0 to 0.5%, 0.001 to 0.1%, 0.001 to 0.09%, or0.001 to 0.05%, or particularly preferably 0.001 to 0.03%. When thecontent of Cl is more than 0.5%, metal wiring is readily eroded at thetime of forming a metal wiring pattern or the like on the tempered glassas well as raising the β-OH value becomes difficult.

Rare earth oxides such as Nb₂O₅ and La₂O₃ are components for enhancingthe Young's modulus. However, the cost of the raw material itself ishigh, and when the rare earth oxides are contained in a large amount,the denitrification resistance is apt to deteriorate. Therefore, thecontent of the rare earth oxides is preferably 3% or less, 2% or less,1% or less, or 0.5% or less, or particularly preferably 0.1% or less.

Because oxides of transition metals such as Co and Ni are componentswhich cause intense coloration of glass, and lower the transmittance, itis desired that the use amount of raw materials and/or cullet of theglass be adjusted so that the content of the oxides of transition metalsfalls within the content ranges of preferably 0.5% or less or 0.1% orless, or particularly preferably 0.05% or less.

It is preferred to use PbO and Bi₂O₃ in an amount as small as possiblefrom the environmental viewpoints, and the content thereof is preferablyless than 0.1%.

The tempered glass of the present invention has a strain point ofpreferably 450° C. or more, 460° C. or more, or 480° C. or more, orparticularly preferably 500° C. or more. The higher the strain point,the more heat resistance is improved, and hence, even if the temperedglass is subjected to a thermal treatment, the compression stress layerdoes not disappear easily. Further, when the strain point is high,stress relaxation does not occur easily during an ion exchangetreatment, with the result that a high compression stress value can beeasily obtained. In addition, when the strain point is high, thetemperature-lowering rate can be increased during thetemperature-lowering process after thermal processing, and hence, theprocess time of the thermal processing can be shortened and productivitycan be enhanced. It should be noted that, in order to increase thestrain point, it is recommended that the content of alkali metal oxidesin the glass composition be decreased, and in particular, the content ofLi₂O be decreased, or the content of alkali earth metal oxides, Al₂O₃,ZrO₂, or P₂O₅, be increased in the glass composition.

The tempered glass of the present invention has a softening point ofpreferably 900° C. or less, 880° C. or less, 860° C. or less, 850° C. orless, 840° C. or less, 830° C. or less, 820° C. or less, 800° C. orless, 780° C. or less, or 770° C. or less, or particularly preferably760° C. or less. The lower the softening point, the lower temperaturethe thermal processing can be performed at. In addition, the lower thesoftening point, the less the loading on a mold becomes when pressmolding is performed. Deterioration of a mold is often caused by aso-called oxidation reaction that is a reaction between metal materialsused in a mold and oxygen in the air. The oxidation reaction allows theformation of a reaction product on the surface of the mold. As a result,press molding does not provide a predetermined shape in some cases.Further, the oxidation reaction allows the reduction of ions in theglass, producing bubbles in some cases. The lower the press moldingtemperature, i.e., the lower the softening point, the more the oxidationreaction can be suppressed. Further, the lower the softening point, thelower the upper values of the press molding temperature and thermalprocessing temperature are made, and hence, the time of an annealingprocess carried out afterward can be shorted.

In the tempered glass of the present invention, the temperaturecorresponding to a viscosity of 10^(2.5) dPa·s is preferably 1600° C. orless, 1550° C. or less, 1500° C. or less, 1450° C. or less, 1430° C. orless, or 1420° C. or less, and particularly preferably 1400° C. or less.When the temperature corresponding to the viscosity of 10^(2.5) dPa·s islower, during melting, burden on a production facility such as a meltingkiln is smaller, and the bubble quality of the glass can be improved.That is, when the temperature corresponding to the viscosity of 10^(2.5)dPa·s is lower, the glass can be produced at lower cost. It should benoted that the temperature corresponding to the viscosity of 10^(2.5)dPa·s corresponds to the melting temperature, and when the temperaturecorresponding to the viscosity of 10^(2.5) dPa·s is lower, the glass canbe melted at a lower temperature. To reduce the temperaturecorresponding to the viscosity of 10^(2.5) dPa·s, the contents of analkali metal oxide, an alkali earth metal oxide, ZnO, B₂O₃, and TiO₂ maybe increased or the contents of SiO₂ and Al₂O₃ may be reduced.

The density of the tempered glass of the present invention is preferably2.7 g/cm³ or less or 2.6 g/cm³ or less, and particularly preferably 2.55g/cm³ or less. As the density becomes lower, the weight of the glass canbe made lighter. The term “density” is a value measured by a knownArchimedes method. To reduce the density, the contents of SiO₂, P₂O₅,and B₂O₃ in the glass composition may be increased or the contents of analkali metal oxide, an alkali earth metal oxide, ZnO, ZrO₂, and TiO₂ maybe reduced.

The thermal expansion coefficient of the tempered glass of the presentinvention is preferably 50 to 110×10⁻⁷/° C., 70 to 110×10⁻⁷/° C., or 75to 105×10⁻⁷/° C., and particularly preferably 80 to 105×10⁻⁷/° C. Whenthe thermal expansion coefficient falls within the above range, itbecomes easier to match with the thermal expansion coefficient of amember such as a metal or an organic adhesive, thereby making itpossible to prevent the separation of the member such as a metal or anorganic adhesive. It should be noted that the thermal expansioncoefficient is increased when the content of an alkali metal oxide or analkali earth metal oxide in the glass composition is increased, whereas,the thermal expansion coefficient is reduced when the content of analkali metal oxide or an alkali earth metal oxide in the glasscomposition is reduced.

In the tempered glass of the present invention, it is preferred that theliquidus temperature be 1200° C. or less, 1050° C. or less, 1000° C. orless, 950° C. or less, or 900° C. or less, and in particular, 860° C. orless. To reduce the liquidus temperature, the contents of Na₂O, K₂O, andB₂O₃ in the glass composition may be increased or the contents of Al₂O₃,Li₂O, MgO, ZnO, TiO₂, and ZrO₂ may be reduced.

In the tempered glass of the present invention, the liquidus viscosityis preferably 10^(4.0) dPa·s or more, 10^(4.5) dPa·s or more, 10^(5.0)dPa·s or more, 10^(5.2) dPa·s or more, 10^(5.3) dPa·s or more, 10^(5.5)dPa·s or more, 10^(5.7) dPa·s or more, or 10^(5.8) dPa·s or more, andparticularly preferably 10^(6.0) dPa·s or more. To raise the liquidusviscosity, the contents of Na₂O and K₂O in the glass composition may beincreased or the contents of Al₂O₃, Li₂O, MgO, ZnO, TiO₂ and ZrO₂ may bereduced. It should be noted that the higher the liquidus viscosity, themore the devitrification resistance and the formability are improved.Further, the lower the liquidus temperature, the more thedevitrification resistance and the formability are improved. That is,the higher the liquidus viscosity, or the lower the liquidustemperature, the more difficult the precipitation of crystals from theglass becomes, and hence, thermal processing can be carried out at lowtemperatures.

The suitable content range and suitable characteristic value of eachcomponent can be appropriately selected and used as a preferred aspect.Of those, the following aspects are more preferred as the tempered glassof the present invention.

(1) A glass composition containing, in terms of mass %, 45 to 75% ofSiO₂, 0 to 30% of Al₂O₃, and 0 to 30% of Li₂O+Na₂O+K₂O, and having aβ-OH value of 0.3 to 1/mm.(2) A glass composition containing, in terms of mass %, 45 to 75% ofSiO₂, 0 to 30% of Al₂O₃, 0 to 4% of B₂O₃, and 0 to 30% of Li₂O+Na₂O+K₂O,and having a β-OH value of 0.3 to 1/mm.(3) A glass composition containing, in terms of mass %, 45 to 75% ofSiO₂, 0 to 30% of Al₂O₃, 0 to 5% of B₂O₃, and 0.1 to 30% ofLi₂O+Na₂O+K₂O, and having a β-OH value of 0.3 to 1/mm.(4) A glass composition containing, in terms of mass %, 45 to 75% ofSiO₂, 0 to 30% of Al₂O₃, 0 to 5% of B₂O₃, 0.1 to 30% of Li₂O+Na₂O+K₂O,and 0 to 0.1% of Cl, and having a β-OH value of 0.3 to 1/mm.(5) A glass composition containing, in terms of mass %, 45 to 75% ofSiO₂, 0 to 30% of Al₂O₃, 0 to 5% of B₂O₃, and 0.1 to 30% ofLi₂O+Na₂O+K₂O, and 0 to 0.01% of Cl, and having a β-OH value of 0.2 to1/mm.(6) A glass composition containing, in terms of mass %, 45 to 75% ofSiO₂, 0 to 30% of Al₂O₃, 0 to 30% of Li₂O+Na₂O+K₂O, and 0 to 0.01% ofCl, and having a β-OH value of 0.3 to 1/mm.(7) A glass composition containing, in terms of mass %, 50 to 75% ofSiO₂, 10 to 20% of Al₂O₃, 0 to 5% of B₂O₃, 0 to 10% of Li₂O, 10 to 20%of Na₂O, 1 to 10% of K₂O, 0.1 to 10% of CaO, 0 to 5% of SrO, 0 to 5% ofBaO, 0 to 0.5% of TiO₂, and 0 to 0.01% of Cl, and having a β-OH value of0.3 to 1/mm.(8) A glass composition containing, in terms of mass %, 50 to 60% ofSiO₂, 12 to 18% of Al₂O₃, 0 to 3% of B₂O₃, 0 to 1% of Li₂O, 10 to 20% ofNa₂O, 1 to 7% of K₂O, 0.1 to 10% of CaO, 0 to 5% of SrO, 0 to 5% of BaO,0 to 0.5% of TiO₂, and 0 to 0.04% of Cl, and having a β-OH value of 0.3to 1/mm.(9) A glass composition containing, in terms of mass %, 50 to 60% ofSiO₂, 12 to 18% of Al₂O₃, 0 to 3% of B₂O₃, 0 to 1% of Li₂O, 10 to 20% ofNa₂O, 1 to 7% of K₂O, 0.1 to 10% of CaO, 0 to 5% of SrO, 0 to 5% of BaO,0 to 0.5% of TiO₂, and 0 to 0.04% of Cl, and having a β-OH value of 0.45to 1/mm.

When using as an exterior part, in order to maintain the mechanicalstrength of the tempered glass, the thickness of the tempered glass ispreferably 0.3 mm or more, 0.5 mm or more, 0.7 mm or more, 1.0 mm ormore, or 1.3 mm or more, and particularly preferably 1.5 mm or more.When using as a substrate, to reduce the weight of the tempered glass,the plate thickness of the tempered glass is preferably 3.0 mm or less,1.5 mm or less, 0.7 mm or less, or 0.5 mm or less, and particularlypreferably 0.3 mm or less.

The tempered glass of the present invention preferably has an unpolishedsurface, and the average surface roughness (Ra) of the unpolishedsurface is preferably 10 Å or less or 5 Å or less, and particularlypreferably 2 Å or less. When using the tempered glass as an exteriorpart having such surface configuration, an appropriate gloss may beimparted to the tempered glass. The term “average surface roughness(Ra)” is a value measured with a method in accordance with the “methodof measuring the surface roughness of an FPD glass substrate” specifiedin SEMI D7-97. Although the theoretical strength of glass is inherentlyvery high, glass is broken even with much lower stress than thetheoretical strength in many cases. This is because a small defectcalled “Griffith flaw” is produced on the surface of the glass in thestep after the forming of molten glass, for example, in the polishingstep. When the surface is unpolished, the inherent mechanical strengthof the glass is hardly impaired, and the glass is hardly broken. Whenthe entire surface (excluding a cut surface) is unpolished, the glass ismore hardly broken. Further, when the surface is unpolished, thepolishing step can be eliminated, thereby making it possible to reducethe production cost of the tempered glass. In the tempered glass of thepresent invention, to prevent breakage from the cut surface, the cutsurface may be chamfered, for example. It should be noted that anunpolished plate-shaped glass having high surface accuracy can beobtained when forming of the molten glass is carried out by the overflowdown-draw method.

The tempered glass of the present invention is preferably formed bysubjecting a glass having a plate shape to thermal processing. Thethermal processing allows easy production of a tempered glass having aspecific shape, and as a result, cost reduction of exterior parts can besought.

The tempered glass of the present invention preferably has a shape otherthan a plate shape, and, for example, preferably has a curved shape, abumpy shape, a wave shape, a stepped shape, or the like. If the temperedglass has any of those shapes, exterior parts having a specific shapecan be applied to some devices equipped with a touch panel.

The tempered glass of the present invention can be produced by placing aglass batch which is prepared to have a predetermined glass compositionin a continuous melting furnace, melting the glass batch by heating at1500 to 1600° C., fining the resultant, feeding the resultant to aforming apparatus, and forming the molten glass, and annealing theglass.

In the tempered glass of the present invention, various forming methodscan be adopted. For example, there may be adopted forming methods, suchas down-draw methods (e.g. an overflow down-draw method, a slot downmethod, and a re-draw method), a float method, and a roll out method. Inaddition, the glass may be directly formed into a curved shape by pressforming.

The tempered glass of the present invention is preferably formed into aplate-shaped glass by an overflow down-draw method. In this way, aplate-shaped glass which is not polished and has good surface qualitycan be produced. The reason therefor is because in the case of adoptingthe overflow down-draw method, a surface to be formed of the glass doesnot come in contact with a trough-shaped refractory, and is formed inthe state of free surface. Here, the overflow down-draw method is suchthat a molten glass is allowed to overflow from both sides of aheat-resistant trough, and the overflown molten glasses are down-drawndownwardly while combining them at the lower end of the trough, tothereby produce a plate-shaped glass. The structure and material of thetrough are not particularly limited as long as they provide desired sizeand surface accuracy of the glass and can realize desired quality.Further, any method may be used to apply force to the glass to performdownward down-draw. For example, there may be adopted a method involvingrotating a heat resistant roll having sufficiently large width in thestate of being in contact with a glass, to thereby draw the glass, and amethod involving allowing several pairs of heat resistant rolls to comeinto contact with only a vicinity of end surfaces of the glass tothereby draw the glass.

The glass of the present invention is characterized by containing, as aglass composition, in terms of mass %, 45 to 75% of SiO₂, 0 to 30% ofAl₂O₃, and 0 to 30% of Li₂O+Na₂O+K₂O and having a β-OH value of 0.3 to1/mm. If the glass is made in such a way as described above, the thermalprocessability of the glass can be improved while its ion exchangeperformance is improved. In addition, the glass of the present inventioncan be provided with technical characteristics (suitable glasscomposition range, suitable properties, remarkable effects, and thelike) similar to those of the tempered glass of the present invention.Here, the description of the technical characteristics is omitted forconvenience sake.

Examples

Hereinafter, the present invention is described in detail according toexamples. Tables 1 and 2 show examples of the present invention (Nos. 1to 8).

TABLE 1 Example No. 1 No. 2 No. 3 No. 4 No. 5 Glass SiO₂ 57.3 57.3 57.357.3 57.3 composition Al₂O₃ 13 13 13 13 13 (mass %) Na₂O 14.5 14.5 14.514.5 14.5 K₂O 4.9 4.9 4.9 4.9 4.9 B₂O₃ 2 2 2 2 2 MgO 2 2 2 2 2 CaO 2 2 22 2 ZrO₂ 4 4 4 4 4 SnO₂ 0.3 0.3 0.3 0.3 0.3 Sb₂O₃ (ppm) 800 800 800 800800 TiO₂ (ppm) 150 150 150 150 150 Cl (ppm) 200 200 200 200 200 β-OH(mm⁻¹) 0.36 0.42 0.55 0.62 0.68 Strain point (° C.) 516 515 508 505 502Annealing point (° C.) 556 555 548 545 542 Softening point (° C.) 758752 746 743 740 10⁴ dPa · s (° C.) 1098 1093 1092 1089 1086 10³ dPa · s(° C.) 1278 1274 1273 1270 1267 10^(2.5) dPa · s (° C.) 1395 1391 13911388 1385 Density (g/cm³) 2.54 2.54 2.54 2.54 2.54 α (×10⁻⁷/° C.) 100100 100 100 100 Liquidus temperature (° C.) 860 860 860 — — Liquidusviscosity (dPa · s) 10^(6.1) 10^(6.1) 10^(6.0) — — Young's modulus (GPa)75 — — — — Compression stress value (MPa) 740 740 740 — — Depth ofcompression stress layer 65 63 60 — — (μm)

TABLE 2 Example No. 6 No. 7 No. 8 Glass composition SiO₂ 56.5 57.5 62.9(mass %) Al₂O₃ 14 16 15 Na₂O 14.5 14.5 13 K₂O 4.9 4.9 5 B₂O₃ 2 1 1 MgO 33 3 CaO 1 1 — ZrO₂ 4 2 — SnO₂ 0.1 0.1 0.1 Sb₂O₃ (ppm) 50 200 50 TiO₂(ppm) 200 100 100 Cl (ppm) 100 100 100 β-OH (mm⁻¹) 0.52 0.58 0.55 Strainpoint (° C.) 518 530 519 Annealing point (° C.) 559 572 564 Softeningpoint (° C.) 762 779 785 10⁴ dPa · s (° C.) 1111 1137 1177 10³ dPa · s(° C.) 1290 1325 1387 10^(2.5) dPa · s (° C.) 1405 1445 1521 Density(g/cm³) 2.54 2.51 2.45 α (×10⁻⁷/° C.) 100 100 94 Compression stressvalue (MPa) 875 834 748 Depth of compression stress 64 66 75 layer (μm)

Each sample in the tables were prepared as follows. First, a glass batchor the like was prepared (for example, the ratio of an oxide rawmaterial to an hydroxide raw material as Al₂O₃ introduction materialswas changed) to achieve the glass composition and the β-OH value shownin the tables, and the resultant was melted at 1580° C. for 8 hours byusing a platinum pot. Next, the molten glass was poured onto a carbonplate and formed into a plate shape. Then, the resultant was opticallypolished. Various properties of the obtained glass were evaluated.

The β-OH value was determined from the above Equation 1 by measuring thetransmittance of glass by FT-IR.

The strain point and the annealing point are values measured based on amethod of ASTM C336.

The softening point is a value measured based on a method of ASTM C338.

Temperatures corresponding to viscosities 10⁴ dPa·s, 10³ dPa·s, and10^(2.5) dPa·s are values measured by a platinum sphere pull up method.

The density is a value measured by a known Archimedes method.

The thermal expansion coefficient is a value measured by a dilatometerand shows an average value in the temperature range of 30 to 380° C.

The liquidus temperature is a value obtained by measuring a temperatureat which a glass is pulverized, a glass powder which passes through astandard sieve of 30 mesh (mesh opening 500 μm) and remaining on 50 mesh(mesh opening 300 μm) is placed in a platinum boat, and kept in atemperature gradient furnace for 24 hours, to thereby deposit crystals.

The liquidus viscosity is a value obtained by measuring the viscosity ofglass at a liquidus temperature by a platinum ball pull up method.

The obtained glass was immersed in a KNO₃ tank maintained at 440° C. for8 hours and an ion exchange treatment was performed. After the ionexchange treatment, the compression stress value and the thickness of acompression stress layer was measured. The compression stress value andthe thickness of the compression stress layer were calculated byobserving the number of interference fringes and the intervals of theinterference fringes using a surface stress meter (FSM-6000 manufacturedby TOSHIBA Corporation). A refractive index was set to 1.52 and a photoelastic constant was set to 28 [(nm/cm)/MPa] for each sample uponcalculation.

As apparent from tables 1 and 2, a softening point is lowered with theincrease in β-OH value, to thereby improve heat processability. As aresult, a tempered glass having a specific shape can be easily obtained.

Note that, in preparing each samples in the tables, a molten glass wasflown, formed into a plate shape, and then the glass was opticallypolished before the ion exchange treatment, for convenience ofexplanation of the present invention. In the case of producing temperedglass in an industrial scale, it is preferred that a plate-shaped glassbe formed by an overflow down-draw method and the like and omit thepolishing treatment, and it is more preferred that an ion exchangetreatment be carried out after the glass is heat processed into aspecific shape.

INDUSTRIAL APPLICABILITY

The tempered glass of the present invention can be used for coverglasses for a mobile phone, a digital camera, a PDA, a touch paneldisplay, and the like, and is suitably used, by taking advantage of itscharacteristics of excellent thermal processability, for exterior partsfor a mobile phone, a mobile PC, a pointing device, and the like, inparticular, for exterior parts having a shape other than a plate shape.Further, the tempered glass of the present invention can be expected tofind applications requiring a high mechanical strength, for example,window glasses, substrates for a magnetic disk, substrates for a flatpanel display, substrates and cover glasses for a solar battery, coverglasses for a solid-state imaging device, and tableware, in addition tothe above-mentioned applications.

1. A tempered glass, comprising, as a glass composition, in terms ofmass %, 45 to 75% of SiO₂, 0 to 30% of Al₂O₃, and 0 to 30% ofLi₂O+Na₂O+K₂O and having a β-OH value of 0.3 to 1/mm.
 2. The temperedglass according to claim 1, comprising, as a glass composition, 0.1 mass% or more of Li₂O+Na₂O+K₂O.
 3. The tempered glass according to claim 1,further comprising, as a glass composition, 0 to 5 mass % of B₂O₃. 4.The tempered glass according to claim 1, wherein: the tempered glasscomprises a compression stress layer on a surface; a compression stressvalue of the compression stress layer is 50 MPa or more; and a thicknessof the compression stress layer is 10 μm or more.
 5. The tempered glassaccording to claim 1, which has a softening point of 900° C. or less. 6.The tempered glass according to claim 1, which has a strain point of400° C. or more.
 7. The tempered glass according to claim 1, which has aliquidus temperature of 1200° C. or less.
 8. The tempered glassaccording to claim 1, which has a liquidus viscosity of 10⁴ dPa·s ormore.
 9. The tempered glass according to claim 1, which has a thermalexpansion coefficient of 50 to 110×10⁻⁷/° C.
 10. The tempered glassaccording to claim 1, which is formed by subjecting a glass having aplate shape to thermal processing.
 11. The tempered glass according toclaim 1, which has a shape other than a plate shape.
 12. A glass,comprising, as a glass composition, in terms of mass %, 45 to 75% ofSiO₂, 0 to 30% of Al₂O₃, and 0 to 30% of Li₂O+Na₂O+K₂O, and having aβ-OH value of 0.3 to 1/mm.
 13. The glass according to claim 12,comprising, as a glass composition, 0.1 mass % or more of Li₂O+Na₂O+K₂O.14. The glass according to claim 12, further comprising, as a glasscomposition, 0 to 5 mass % of B₂O₃.
 15. The glass according to claim 12,which has a softening point of 900° C. or less.
 16. The glass accordingto claim 12, which has a strain point of 400° C. or more.
 17. The glassaccording to claim 12, which has a liquidus temperature of 1200° C. orless.
 18. The glass according to claim 12, which has a liquidusviscosity of 10⁴ dPa·s or more.
 19. The glass according to claim 12,which has a thermal expansion coefficient of 50 to 110×10⁻⁷/° C.
 20. Theglass according to claim 12, which has been subjected to thermalprocessing.
 21. The glass according to claim 12, which has a shape otherthan a plate shape.